CN102976876B - Polyisobutylene succinimide quaternary ammonium salt emulsifier and preparation method thereof - Google Patents
Polyisobutylene succinimide quaternary ammonium salt emulsifier and preparation method thereof Download PDFInfo
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- CN102976876B CN102976876B CN201210509433.0A CN201210509433A CN102976876B CN 102976876 B CN102976876 B CN 102976876B CN 201210509433 A CN201210509433 A CN 201210509433A CN 102976876 B CN102976876 B CN 102976876B
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Abstract
The invention provides a polyisobutylene succinimide quaternary ammonium salt emulsifier and a preparation method thereof. The preparation method comprises the following steps: performing amination reaction on polyisobutylene succinic anhydride and an amination reagent to obtain polyisobutylene succinimide; and then, performing quaternization reaction on the polyisobutylene succinimide and a quaternization reagent to obtain the polyisobutylene succinimide quaternary ammonium salt emulsifier. The emulsifier has fine stability quality and is used for the preparation of an emulsion explosive in the emulsion explosive industry.
Description
Technical field
The present invention relates to explosive emulsifying agent, particularly relate to a kind of Polyisobutylene succinimide quaternary ammonium salt emulsifier of producing emulsion explosive and preparation method thereof.
Background technology
Emulsifying agent plays critical effect in emulsion explosive, and emulsifying agent makes oxygenant aqueous phase and fuel oil phase form oil-in-water emulsify explosive matrix, and the performance of emulsifying agent decides the blast performance of emulsion explosive and storge quality etc.
At present, use emulsifying agent mainly SPAN-80 and polybutene succinimide (singly to hang, two extension and hang) two class emulsifying agents more widely in the production of emulsion explosive more.The advantage of SPAN-80 is easy newborn better performances, namely just can play breast at lower rotating speed, but containing double bond in its molecular structure, oxidized rear easy breakdown of emulsion, crystallization, make the emulsion explosive storage time prepared therefrom relatively short.And the advantage of polybutene succinimide class emulsifying agent to be emulsion explosive prepared therefrom comparatively stable, the storage time is relatively long, is generally half a year more than.But emulsifying property is relatively poor, more difficult emulsifying effect.For ensureing emulsifying property and the stability of emulsifying agent, normal by used in combination for above-mentioned two kinds of emulsifying agents in production.Macromolecule emulsifier (T152) is as most typical polybutene succinimide class emulsifying agent, normal and the composite use of SPAN-80 in production, but contriver finds after deliberation, the stability of the emulsifying agent after composite use is still not fully up to expectations, therefore invents a kind of stability better polybutene succinimide class emulsifying agent and has great importance.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of stability excellent, is applicable to the emulsifying agent of Preparation and storage time longer emulsion explosive, and the preparation method of this emulsifying agent.
For solving the problems of the technologies described above, the present invention is achieved through the following technical solutions:
A kind of Polyisobutylene succinimide quaternary ammonium salt emulsifier, described Polyisobutylene succinimide quaternary ammonium salt emulsifier is prepared like this: get polyisobutylene butanedioic anhydride and amination reagent and carry out amination reaction and obtain polyisobutene succinimide, gained polyisobutene succinimide carries out quaterisation with quaternizing agent again, to obtain final product.
In aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, the mol ratio of described polyisobutylene butanedioic anhydride and aminating agent is 1.0:0.95-1.0:1.2; The mol ratio of described polyisobutene succinimide and quaternizing agent is 1.0:0.95-1.0:1.5.
In aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, described amination reaction process also adds amination thinning oil, and described amination thinning oil is organic solvent.
Above-mentioned organic solvent is toluene, dimethylbenzene, octane, nonane, certain herbaceous plants with big flowers alkane, white mineral oil, machinery oil or base oil.Wherein, when thinning oil is white mineral oil, machinery oil or base oil, the amount added is the 30%-50% of polyisobutylene butanedioic anhydride quality.When thinning oil is toluene, dimethylbenzene, octane, nonane or certain herbaceous plants with big flowers alkane, the amount added is the 50%-200% of polyisobutylene butanedioic anhydride quality.
In aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, described quaterisation process also adds quaternized thinning oil, and described quaternized thinning oil is organic solvent, or the mixed solvent of organic solvent and ethanol or Virahol.
The mass ratio of above-mentioned organic solvent and ethanol or Virahol is 1.0:0.25-1.0:2.0.
Above-mentioned organic solvent is toluene, dimethylbenzene, octane, nonane, certain herbaceous plants with big flowers alkane, white mineral oil, machinery oil or base oil.The addition of organic solvent is to maintain amination reaction.
In aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, the molecular weight of described polyisobutylene butanedioic anhydride is 500-3000.
Specifically, the molecular weight of described polyisobutylene butanedioic anhydride is 800-2000.
More particularly, the molecular weight of described polyisobutylene butanedioic anhydride is 1000-1500.
In aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, described amination reagent is: the Diamines material simultaneously in molecule with primary amine group and tertiary amine group.
Specifically, described amination reagent is: N, N-dimethyl-1,3-propylene diamine, N, N-dimethyl-1，2-diaminoethane, N, N-diethyl-1,3-propylene diamine or N, N-dimethyl-p-phenylenediamine.
More particularly, described amination reagent is: N, N-dimethyl-1,3-propylene diamine.
In aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, described quaternizing agent is methyl-sulfate, ethyl sulfate, 3-chlorine-1,2-propylene glycol, sodium chloroacetate, chloroethyl sodium sulfonate or bromotrifluoromethane sodium sulfonate.
Specifically, described quaternizing agent is ethyl sulfate, 3-chlorine-1,2-propylene glycol, sodium chloroacetate or chloroethyl sodium sulfonate.
The preparation method of aforesaid Polyisobutylene succinimide quaternary ammonium salt emulsifier, comprises the following steps:
1. amination reaction process: polyisobutylene butanedioic anhydride is dropped into reactor, add thinning oil, stir, be warming up to 30-80 DEG C, drip amination reagent, after dropwising, after continuing reaction 0.5-2.0h, be warming up to 100-180 DEG C, under vacuum tightness is 0.02MPa-0.09MPa, when reacting substantially constant to acid number, terminate reaction, obtain polyisobutene succinimide;
2. quaterisation process: the step polyisobutene succinimide that 1. amination reaction obtains is dropped into reactor, add thinning oil, when being warming up to 50-100 DEG C, drip quaternizing agent, aneroid quaternizing agent is first dissolved in solvent and drips, after dropwising, continue to terminate reaction when reaction is substantially constant to amine value, to obtain final product.
In the present invention, amination reaction and quaterisation process add thinning oil, are more conducive to reactant and fully mix.
In the present invention, according to the physical property Determines feeding manner of quaternizing agent, for methyl-sulfate, ethyl sulfate, the liquid quaternary ammonium reagent such as 3-chlorine-1,2-propylene glycol can directly charging, for sodium chloroacetate, chloroethyl sodium sulfonate, the solid quaternizing agents such as bromotrifluoromethane sodium sulfonate are then dissolved in water and form solution charging again.
Beneficial effect of the present invention: emulsifying agent stability prepared by the present invention is excellent, is applicable to emulsion explosive industry and prepares emulsion explosive.
Applicant carried out following experiments, provable the present invention has useful effect:
Experimental example 1:
One, the preparation of emulsifying agent
P1: according to method preparation described in the embodiment of the present invention 1.
P2: according to method preparation described in the embodiment of the present invention 2.
P3: according to method preparation described in the embodiment of the present invention 3.
P4: according to method preparation described in the embodiment of the present invention 4.
T152: Lanzhou Lubrizol Corp. produces.
Note: sample activity thing content prepared by above-mentioned 4 embodiments is different, but is all diluted to the concentration identical with T152 when using.
Two, the macromolecule emulsifier (T152) in tested recipe is replaced to prepare emulsion matrix, (tested recipe: ammonium nitrate 78%, SODIUMNITRATE 5.5%, water 10%, compound wax 4%, sp-80 emulsifying agent 1.5%, T152 macromolecule emulsifier 1%) emulsifying agent of appeal preparation.Measure the stability of emulsion matrix by high/low temperature circulation method, to characterize its stability in storage, emulsifying agent performance is as being shown in Table 1.
Table 1 emulsion matrix stability
As can be seen from Table 1, emulsifying agent prepared by the method for the invention, stability is all better than macromolecule emulsifier (T152), it is the more excellent polybutene succinimide class emulsifying agent of a kind of stability, macromolecule emulsifier (T152) can be replaced to use, be applicable to the emulsion explosive of Preparation and storage time length.
Figure of description
Fig. 1 is the infrared spectrogram of polyisobutylene butanedioic anhydride.2960cm
-1and 2894.cm
-1the neighbouring absorption peak occurred is the stretching vibration absorption peak of methyl and methylene radical, 1472cm
-1neighbouring is methylene radical flexural vibration peaks, 1389cm
-1and 1366cm
-1near be the characteristic peak of the tertiary butyl, 1866.1cm
-1and 1786.9cm
-1neighbouring is the asymmetric of five-membered cyclic acid anhydrides and symmetrical stretching vibration peak, is the charateristic avsorption band of polyisobutylene butanedioic anhydride.
Fig. 2 is the infrared spectrogram of polyisobutene succinimide.Compared to Figure 1, maximum difference is 1866.1cm
-1and 1786.9cm
-1asymmetric and the symmetrical stretching vibration peak of neighbouring five-membered cyclic acid anhydrides disappears, and has occurred 1774.8cm
-1and 1707.7cm
-1two groups of absorption peaks, this is the pentacyclic charateristic avsorption band of succimide, and the infrared spectrogram of having synthesized polyisobutene succinimide is described.
Fig. 3 is the infrared spectrogram of embodiment product.Compared with Fig. 2, main difference is 3359.7cm
-1the neighbouring absorption peak occurring a group wide, is the absorption peak of hydroxyl, the product having synthesized embodiment 2 is described.
Embodiment
Embodiment 1
Be polyisobutylene butanedioic anhydride (Mn=1030g/mol) 82.4g (0.08mol) of 108.86mg/gKOH by saponification value, base oil 33.0g drops into reactor, by N, N-dimethyl-1, 3-propylene diamine 8.0g(0.078mol) be added to dropping funnel, stir, be warming up to 40 DEG C, drip N, N-dimethyl-1, 3-propylene diamine, after dropwising, after continuing reaction 1.0h, be warming up to about 130 ~ 150 DEG C, under vacuum tightness is 0.08MPa, when reacting substantially constant to acid number, terminate reaction, obtain polyisobutene succinimide, add base oil 5.7g, base oil is made to account for 30% of heavy amount.
Polyisobutene succinimide product 79.5g(0.05mol by above-mentioned preparation) drop into reactor, by ethyl sulfate 8.5g(0.055mol) be added to dropping funnel, stir, be warming up to about 80 DEG C, drip ethyl sulfate, after dropwising, continue to be reacted to amine value substantially constant time terminate reaction, obtain described emulsifying agent P1, add base oil 3.6g, make active matter content be about 70%.
Embodiment 2
Polyisobutene succinimide 79.5g(0.05mol by preparing according to method described in embodiment 1) drop into reactor, by 3-chlorine-1,2-propylene glycol 6.1g(0.055mol) be added to dropping funnel, stir, be warming up to about 80 DEG C, drip 3-chlorine-1,2-propylene glycol, after dropwising, continue to be reacted to amine value substantially constant time terminate reaction, obtain described emulsifying agent P2, add base oil 2.6g, make active matter content be about 70%.
Embodiment 3
Be polyisobutylene butanedioic anhydride (Mn=1030g/mol) 82.4g (0.08mol) of 108.86mg/gKOH by saponification value, octane 80g drops into reactor, by N, N-dimethyl-1,3-propylene diamine 9.0g (0.088mol) is added to dropping funnel, stirs, be warming up to 50 DEG C, drip N, N-dimethyl-1,3-propylene diamine, after dropwising, after continuing reaction 0.5h, be warming up to about 130 DEG C, under vacuum tightness is 0.04MPa, when reacting substantially constant to acid number, terminate reaction, except desolventizing, obtain polyisobutene succinimide.
Polyisobutene succinimide 55.7g(0.05mol by above-mentioned preparation), octane 60g, Virahol 30g drop into reactor, with 15g water by 7.0g(0.06mol) sodium chloroacetate dissolved, and be added to dropping funnel, stir, be warming up to about 80 DEG C, drip sodium chloroacetate solution, after dropwising, continue to be reacted to amine value substantially constant time terminate reaction, except desolventizing, obtain described emulsifying agent P3, add base oil 25.0g, make Product Activity thing content be about 70%.
Embodiment 4
Polyisobutene succinimide 55.7g(0.05mol by preparing according to method described in embodiment 3), octane 60g, Virahol 40g drops into reactor, with 25g water by 10.2g(0.06mol) dissolving of chloroethyl sodium sulfonate, and be added to dropping funnel, stir, be warming up to about 80 DEG C, drip chloroethyl sodium sulfonate solution, after dropwising, continue to be reacted to amine value substantially constant time terminate reaction, except desolventizing, obtain described emulsifying agent P4, add base oil 26.0g, make Product Activity thing content be about 70%.
The present invention is not restricted to the described embodiments, and can determine concrete embodiment according to technical scheme of the present invention and practical situation.
Claims (3)
1. a Polyisobutylene succinimide quaternary ammonium salt emulsifier, it is characterized in that: described Polyisobutylene succinimide quaternary ammonium salt emulsifier is prepared like this: get polyisobutylene butanedioic anhydride and amination reagent and carry out amination reaction and obtain polyisobutene succinimide, gained polyisobutene succinimide carries out quaterisation with quaternizing agent again, to obtain final product;
The mol ratio of described polyisobutylene butanedioic anhydride and aminating agent is 1.0:0.95-1.0:1.2; The mol ratio of described polyisobutene succinimide and quaternizing agent is 1.0:0.95-1.0:1.5;
Described amination reaction process also adds amination thinning oil, and described amination thinning oil is organic solvent;
Described quaterisation process also adds quaternized thinning oil, and described quaternized thinning oil is organic solvent, or the mixed solvent of organic solvent and ethanol or Virahol; The mass ratio of described organic solvent and ethanol or Virahol is 1.0:0.25-1.0:2.0;
Described organic solvent is toluene, dimethylbenzene, octane, nonane, certain herbaceous plants with big flowers alkane, white mineral oil, machinery oil or base oil;
Described amination reagent is: the Diamines material simultaneously in molecule with primary amine group and tertiary amine group;
Described quaternizing agent is methyl-sulfate, ethyl sulfate, 3-chlorine-1,2-propylene glycol, sodium chloroacetate, chloroethyl sodium sulfonate or bromotrifluoromethane sodium sulfonate.
2. Polyisobutylene succinimide quaternary ammonium salt emulsifier according to claim 1, is characterized in that: the molecular weight of described polyisobutylene butanedioic anhydride is 500-3000.
3. prepare the preparation method of Polyisobutylene succinimide quaternary ammonium salt emulsifier described in claim 1, it is characterized in that, comprise the following steps:
1. amination reaction process: polyisobutylene butanedioic anhydride is dropped into reactor, add thinning oil, stir, be warming up to 30-80 DEG C, drip amination reagent, after dropwising, after continuing reaction 0.5-2.0h, be warming up to 100-180 DEG C, under vacuum tightness is 0.02MPa-0.09MPa, when reacting substantially constant to acid number, terminate reaction, obtain polyisobutene succinimide;
2. quaterisation process: the step polyisobutene succinimide that 1. amination reaction obtains is dropped into reactor, add thinning oil, when being warming up to 50-100 DEG C, drip quaternizing agent, aneroid quaternizing agent is first dissolved in solvent and drips, after dropwising, continue to terminate reaction when reaction is substantially constant to amine value, to obtain final product.
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| WO2020120323A1 (en) * | 2018-12-10 | 2020-06-18 | Solenis Technologies Cayman, L.P. | Stabilisers for use in inverse emulsion polymerisation processes |
| RU2808653C2 (en) * | 2018-12-10 | 2023-11-30 | Соленис Текнолоджиз Кеймэн, Л.П. | Stabilizers intended for use in reverse emulsion polymerization methods |
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| AU2015267144B2 (en) * | 2014-05-30 | 2019-06-13 | The Lubrizol Corporation | Low molecular weight amide/ester containing quaternary ammonium salts |
| WO2019018763A1 (en) * | 2017-07-21 | 2019-01-24 | Exxonmobil Research And Engineering Company | Lubricating compositions with enhanced deposit performance |
| CN110357749B (en) * | 2019-07-31 | 2021-02-26 | 北矿亿博(沧州)科技有限责任公司 | Emulsifier for emulsion explosive, preparation method thereof, emulsion matrix and emulsion explosive |
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| WO2020120323A1 (en) * | 2018-12-10 | 2020-06-18 | Solenis Technologies Cayman, L.P. | Stabilisers for use in inverse emulsion polymerisation processes |
| RU2808653C2 (en) * | 2018-12-10 | 2023-11-30 | Соленис Текнолоджиз Кеймэн, Л.П. | Stabilizers intended for use in reverse emulsion polymerization methods |
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